NZ328222A - Green soda-lime-silica glass containing selenium, chromium trioxide and iron and cobalt oxides - Google Patents

Abstract

The present invention provides a green colored, infrared and ultraviolet absorbing glass article having a luminous transmittance of up to 60 percent. The composition of the glass article uses a standard soda-lime-silica glass base composition and additionally iron, cobalt, selenium, and chromium, and optionally titanium, as infrared and ultraviolet radiation absorbing materials and colorants. The glasses of the present invention have a color characterized by a dominant wavelength in the range of about 480 to 565 nanometers, preferably about 495 to 560 nanometers, with an excitation purity of no higher than about 20 percent, preferably no higher than about 10 percent, and more preferably no higher than about 7 percent. The glass compositions may be provided with different levels of spectral performance depending on the particular application and desired luminous transmittance. In one embodiment of the invention, the glass composition of a green colored, infrared and ultraviolet radiation absorbing soda-lime-silica glass article includes a solar radiation absorbing and colorant portion consisting essentially of about 0.60 to 4 percent by weight total iron, about 0.13 to 0.9 percent by weight FeO, about 40 to 500 PPM CoO, about 5 to 70 PPM Se, about 15 to 800 PPM Cr2O3, and about 0.02 to 1 percent by weight TiO2. In another embodiment of the invention, the glass composition of the article includes a solar radiation absorbing and colorant portion consisting essentially of 1 to less than 1.4 percent by weight total iron, about 0.2 to 0.6 percent by weight FeO, greater than 200 to about 500 PPM CoO, about 5 to 70 PPM Se, greater than 200 to about 800 PPM Cr2O3, and 0 to about 1 percent by weight TiO2.

Description

New Zealand Paient Spedficaiion for Paient Number 328222 New Zealand No. International No. 328222 PCT/ TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION Priority dates: 02.07.1996;04.06.1997; Complete Specification Filed: 02.07.1997 Classification:^) C03C4/02// C03C3/087 Publication date: 25 March 1998 Journal No.: 1426 NO DRAWINGS NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Green privacy glass Name, address and nationality of applicant(s) as in international application form: PPG INDUSTRIES, INC., a Pennsylvania corporation of One PPG Place, Pittsburgh, Pennsylvania 15272, United States of America 328 2 2 2 NEW ZEALAND PATENTS ACT, 1953 No: Date: COMPLETE SPECIFICATION GREEN PRIVACY GLASS We, PPG INDUSTRIES, INC., a corporation organized under the laws of the Commonwealth of Pennsylvania, United States of America, of One PPG Place, Pittsburgh, Pennsylvania 15272, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: 328222 - 1a - This application claims the benefit of U.S. Provisional Application No. 60/021,034, filed July 2, 1996.

BACKGROUND OF THE INVENTION This invention relates to a tinted, green colored soda-lime-silica glass having a low luminous transmittance that makes it highly desirable for use as a privacy glazing in vehicles, such as the side and rear windows in vans. In particular, the glass has a luminous transmittance of 60 percent or less, preferably between about 10 to 40 percent. As used herein, the term "green colored" is meant to include glasses that have a dominant wavelength of about 480 to 565 nanometers (nm) and may be characterized as green blue, green yellow or green gray in color. In addition, the glass of the present invention generally exhibits lower infrared and ultraviolet radiation transmittance when compared to typical green glasses used in automotive applications. The glass is also compatible with float glass manufacturing methods.

Various dark tinted, infrared and ultraviolet radiation absorbing glass compositions are known in the art. The primary colorant in typical dark tinted automotive privacy glasses is iron, which is usually present in both the Fe203 and FeO forms. Some glasses use cobalt, selenium and, optionally, nickel in combination with iron to further control infrared and ultraviolet radiation and color, for example as disclosed in U.S. Patent Nos. 4,873,206 to Jones; 5,278,108 to Cheng et al.; 5,308,805 to Baker et al.; and 5,393,593 to Gulotta et al., and European Patent application EP 0 705 800. Others also include chromium with thisj combination of colorants as disclosed in U.S. Patent Nos. 4,104,Q76^to 7 2 Pons; 4,339,541 to Dela Ruye; 5,023,210 to Krumwiede et al; ancL_ 13&/ ,352,640 to Combes et al.; European Patent application EP 0 536HD4.9; French Patent 2,331,527 and Canadian Patent 2,148,954. Still, other / <? glasses may include additional materials, such as disclosed in WO 96/00194, which teaches the inclusion of fluorine, zirconium, zinc, cerium, titanium and copper in the glass composition and requires that the sum of the alkaline earth oxides be less than 10 wt.% of the glass.

In producing infrared and ultraviolet radiation absorbing glasses, the relative amounts of iron and other additives must be closely monitored and controlled within an operating range to provide the desired color and spectral properties. It would be desirable to have a dark tinted green colored glass that may be used as a privacy glazing for vehicles to 10 complement the green colored glasses typically used in automobiles that exhibits superior solar performance properties and is compatible with commercial float glass manufacturing techniques.

SUMMARY OF THE INVENTION 15 The present invention provides a green colored, infrared and ultraviolet absorbing glass article having a luminous transmittance of up to 60 percent. The composition of the glass article uses a standard soda-lime-silica glass base composition and additionally iron, cobalt, selenium, and chromium, and optionally titanium, as infrared and ultraviolet radiation 20 absorbing materials and colorants. The preferred glasses of the present invention have a color characterized by a dominant wavelength in the range of about 480 to 565 nanometers, preferably about 495 to 560 nanometers, with an excitation purity of no higher than about 20%, preferably no higher than about 10%, and more preferably no higher than about 7%. 25 The glass compositions may be provided with different levels of spectral performance depending on the particular application and desired luminous transmittance.

In one embodiment of the invention, the glass composition of a green colored, infrared and ultraviolet radiation absorbing soda-lime-silica B B Q 11 V B ollaatuni w Intfillaatuni 1 3 m !§98 of New Zoalsnd 328 22 glass article includes a solar radiation absorbing and colorant portion consisting essentially of about 0.60 to 4 percent by weight total iron, about 0.13 to 0.9 percent by weight FeO, about 40 to 500 PPM CoO, about 5 to 70 PPM Se, about 15 to 800 PPM Cr203, and about 0.02 to 1 5 percent by weight Ti02. In another embodiment of the invention, the glass composition of the article includes a solar radiation absorbing and colorant portion consisting essentially of 1 to less than 1.4 percent by weight total iron, about 0.2 to 0.6 percent by weight FeO, greater than 200 to about 500 PPM CoO, about 5 to 70 PPM Se, greater than 200 to 10 about 800 PPM Cr203, and 0 to about 1 percent by weight Ti02.

DFTAILED DESCRIPTION OF THE INVENTION The base glass of the present invention, that is, the major constituents of the glass without infrared or ultraviolet absorbing materials 15 and/or colorants, which are the object of the present invention, is commercial soda-lime-silica glass characterized as follows: Weight Percent Si02 66-75 Na20 10-20 CaO 5-15 MgO 0-5 AI2Og 0-5 K20 0-5 As used herein, all "weight percent (wt.%)" values are based on the total weight of the final glass composition.

To this base glass, the present invention adds infrared and_ ultraviolet radiation absorbing materials and colorants in the formjSf^ronTT^ cobalt, selenium, chromium and, optionally, titanium. As disclosed herein, / -Jul. 1897 iron is expressed in terms of Fe203 and FeO, cobalt is expressed in terms 328222 of CoO, selenium is expressed in terms of elemental Se, chromium is expressed in terms of Cr203 and titanium is expressed in terms of Ti02. It should be appreciated that the glass compositions disclosed herein may include small amounts of other materials, for example melting and refining 5 aids, tramp materials or impurities. It should be further appreciated that in one embodiment of the invention, small amounts of additional materials may be included in the glass to improve the solar performance of the glass as will be discussed later in more detail.

The iron oxides in a glass composition perform several functions. 10 Ferric oxide, Fe203, is a strong ultraviolet radiation absorber and operates as a yellow colorant in the glass. Ferrous oxide, FeO, is a strong infrared radiation absorber and operates as a blue colorant. The total amount of iron present in the glasses disclosed herein is expressed in terms of Fe203 in accordance with standard analytical practice but that does not imply 15 that all of the iron is actually in the form of Fe203. Likewise, the amount of iron in the ferrous state is reported as FeO, even though it may not actually be present in the glass as FeO. In order to reflect the relative amounts of ferrous and ferric iron in the glass compositions disclosed herein, the term "redox" shall mean the amount of iron in the ferrous state 20 (expressed as FeO) divided by the amount of total iron (expressed as Fe203). Furthermore, unless stated otherwise, the term "total iron" in this specification shall mean total iron expressed in terms of Fe203 and the term "FeO" shall mean iron in the ferrous state expressed in terms of FeO.

Sa is an ultraviolet and infrared radiation absorbing colorant that 25 imparts a pink or brown color to soda-lime-silica glass. Se may also absorb some infrared radiation and its use tends to decrease redox. CoO operates as a blue colorant and does not exhibit any appreciable ultraviolet or infrared radiation absorbing properties. Cr203 imparts a green color to the glass and helps control the final glass color. It is believed that the 2 - JUL 1937 328 2 2 2 chromium may also provide some ultraviolet radiation absorption. Ti02 is an ultraviolet radiation absorber that operates as a colorant imparting a yellow color to the glass composition. A proper balance between the iron, i.e. ferric and ferrous oxides, chromium, selenium, cobalt and optionally 5 titanium content is required to obtain the desired green colored privacy glass with the desired spectral properties.

The glass of the present invention may be melted and refined in a continuous, large-scale, commercial melting operation and formed into flat glass sheets of varying thicknesses by the float method in which the 10 molten glass is supported on a pool of molten metal, usually tin, as it assumes a ribbon shape and is cooled. It should be appreciated that as a result of forming the glass on molten tin, measurable amounts of tin oxide may migrate into surface portions of the glass on the side that was in contact with the tin. Typically, a piece of float glass has an Sn02 15 concentration of at least 0.05 to 2 wt.% in the first 25 microns below the surface of the glass that was in contact with the tin. Typical background levels of Sn02 may be as high as 30 parts per million (PPM).

The melting and forming arrangements used to produce the glass compositions of the present invention include, but are not limited to a 20 conventional, overhead fired continuous melting operation, as is well known in the art, or a multi-stage melting operation, as disclosed in U.S.

Patent Nos. 4,381,934 to Kunkle et al.; 4,792,536 to Pecoraro et al. and 4,886,539 to Cerutti et al. If required, a.stirring arrangement may be employed within the melting and/or forming stages of the glass production 25 operation to homogenize the glass in order to produce glass of the highest optical quality.

Tables 1, 2 and 3 illustrate examples of glass compositions which embody the principles of the present invention. The examples ^TTaEleiS~1 and 2 are computer modeled compositions generated by a glas(s colqr and i 2 " JUL w IK 32 8 2 2 1 10 15 • 20 spectral performance computer model developed by PPG Industries, Inc. The examples In Tabie 3 are actual experimental laboratory melts. The spectral properties shown for Tables 1 and 3 are based on a reference thickness of 0.160 inches (4.06 mm) and those in Table 2 are based on a reference thickness of 0.154 inches (3.91 mm). For comparison purposes, the spectral properties of the examples may be approximated at different thicknesses using the formulas disclosed in U.S..Patent No. 4,792,536. Only the iron, cobalt, selenium, chromium and titanium portions of the examples are listed in the tables. With respect to the transmittance data provided in the tables, the luminous transmittance (LTA) is measured using C.I.E. standard illuminant "A" with a 2° observer over the wavelength range 380 to 770 nanometers and glass color, in terms of dominant wavelength and excitation purity, is measured using C.I.E. standard illuminant "C" with a 2° observer, following the procedures established in ASTM E308-90. The total solar ultraviolet transmittance (TSUV ) is measured over the wavelength range 300 to 400 nanometers, total solar infrared transmittance (TSIR) is measured over the wavelength range 720 to 2000 nanometers, and total solar energy transmittance (TSET) is measured over the wavelength range 300 to 2000 nanometers. The TSUV, TSIR and TSET transmittance data are calculated using Parry Moon air mass 2.0 direct solar irradiance data and integrated using the Trapezoidal Rule, as is known in the art.

The optical properties reported in Tables 1 and 2 are the expected properties of a glass having a base glass composition and colorants, generally as discussed herein, based upon the absorption coefficients of the glass' constituents, assuming that the glass is homogeneous throughout and is manufactured by a conventional float glass process, as is well known in the art. ' P 328222 The information provided in Table 3 is based on experimental laboratory melts having approximately the following batch components: cullet A 125 gm cullet B 22.32 gm cullet C 8.93 gm rouge 0.32 gm Cr203 0.0461 gm CM O i— 0.3-0.6 gm Se 0.0037-0.0073 gm graphite 0.015 gm The cullets used in the melts included varying amounts of iron, cobalt, selenium, chromium and/or titanium. More specifically, cullet A included 0.811 wt.% total iron, 0.212 wt.% FeO, 101 PPM CoO, 17 PPM Se, 8 PPM Cr203, and 0.02 wt.% Ti02. Cullet B included 1.417 wt.% total 15 iron, 0.362 wt.% FeO, 211.25 PPM CoO, 25 PPM Se, and 7.5 PPM Cr203. Cullet C included 0.93 wt.% total iron, 0.24 wt.% FeO, 6 PPM Cr203/ and 0.02 wt.% Ti02. In preparing the melts, the ingredients were weighed out and mixed. It is believed that the material was then placed in a 4-inch platinum crucible and heated to 2600°F (1427°C) for 30 minutes 20 and then heated to 2650°F (1454°C) for 1 hour. Next, the molten glass was fritted in water, dried, put in a 2-inch platinum crucible and reheated at 2650°F (1454°C) for at least 1 hour. The molten glass was then poured out of the crucible to form a slab and annealed. Samples were cut from the slab and ground and polished for analysis. The chemical analysis 25 of the glass compositions was determined using a RIGAKU 3370 X-ray fluorescence spectrophotometer. The FeO content was determined using wet chemistry techniques, as is well known in the art. The spectral characteristics of the glass were determined on annealed|samptes using a-^.

Perkin-EImer Lambda 9 UV/VIS/NIR spectrophotometer prior to tempering I 2 - JUL 1S97 j 197 f':-pUV£D 328222 the glass or prolonged exposure to ultraviolet radiation, which will effect the spectral properties of the glass.

The following is representative of the basic oxides of the particular experimental melts disclosed in Table 3, which also fall within the base glass composition discussed earlier: Si02 70-72 wt.% Na20 12-14 wt.% CaO 8-10 wt.% MgO 3-4 wt.% AI2O3 0.1-0.6 wt.% k2o 0.01-0.15 wt.% The analysis of these melts also showed that the glasses included about 0.081 wt.% MnOz. It is presumed that the Mn02 entered into the glass melt as part of the cullet.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 FeO (wt.%) 0.4320 0.5580 0.7240 0.4775 0.5225 0.5143 0.5670 0.6545 0.6110 0.4725 0.6938 0.5980 Total iron (wt.%) 1.920 1.860 1.810 1.910 1.900 1.870 1.890 1.870 1.880 1.890 1.850 1.840 Model redox 0.2250 0.3000 0.4000 0.2500 0.2750 0.2750 0.3000 0.3500 0.3250 0.2500 0.3750 0.3250 Cr203 (wt.%) 0.0365 0.0350 0.0350 0.0365 0.0365 0.0340 0.0365 0.0370 0.0365 0.0350 0.0370 0.0355 CoO (wt.%) 0.0391 0.0356 0.0310 0.0377 0.0364 0.0370 0.0351 0.0326 0.0338 0.0379 0.0314 0.0344 Se (wt.%) 0.0047 0.0050 0.0054 0.0048 0.0049 0.0048 0.0050 0.0052 0.0051 0.0047 0.0053 0.0050 Ti02 (wt.%) 0.1800 0.2400 0.4900 0.3400 0.4400 LTA {%) .02 .04 .05 .05 .06 .08 .08 .10 .10 .12 .12 .13 TSUV (%) 2.48 2.88 3.58 2.62 2.77 2.59 2.94 3.29 3.11 2.52 3.51 2.95 TSIR (%) 7.28 3.84 1.73 .76 4.59 4.78 3.68 2.41 2.97 .91 2.00 3.16 TSET (%) 6.33 4.42 3.18 .50 4.85 4.96 4.33 3.60 3.93 .61 3.37 4.05 DW (nm) 551.02 550.90 550.96 551.29 550.79 550.61 550.68 550.52 550.92 550.76 550.81 550.64 Pe (%) 3.58 3.57 3.62 3.72 3.72 3.85 3.76 3.85 3.84 3.86 3.83 3.98 TABLE 1 (cont.) Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 FeO (wt.%) 0.7360 0.4298 0.6825 0.6405 0.3860 0.3860 0.3750 0.3750 0.8750 0.3750 0.8125 0.3750 Total iron (wt.%) 1.840 1.910 1.820 1.830 1.930 1.930 1.500 1.500 3.500 1.500 3.250 1.500 Model redox 0.4000 0.2250 0.3750 0.3500 0.2000 0.2000 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 Cr203 (wt.%) 0.0370 0.0340 0.0340 0.0345 0.0375 0.0330 0.0250 0.0250 0.0250 0.0250 0.0250 0.0250 CoO (wt.%) 0.0302 0.0390 0.0320 0.0330 0.0398 0.0400 0.0450 0.0400 0.0220 0.0220 0.0220 0.0350 Se (wt.%) 0.0054 0.0046 0.0052 0.0051 0.0045 0.0044 0.0027 0.0027 0.0027 0.0060 0.0027 0.0027 Ti02 (wt.%) 0.2600 0.4500 0.3900 0.3900 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) .13 .15 .16 .19 .20 .28 6.54 7.80 8.59 8.73 9.20 9.33 TSUV"(%); 3.72 2.41 3.29 3.16 j o 2.24 6.17 6.21 1.07 2.86 1.32 6.24 TSIR (%) / 1.64 7.38 2.11 2.58 9.28 9.29 9.94 3.99 0.89 9.98 1.18 .04 T§ET (%) 3.16 6.44 3.44 3.73 7.50 7.54 9.18 9.65 3.64 9.09 4.10 .20 dw (nm) 551.01 550.93 550.70 550.93 550.63 550.86 478.05 479.92 549.82 581.29 549.90 482.49 F?(%) : 3.86 3.70 3.89 3.92 3.76 3.89 .19 23.61 18.23 38.27 16.69 16.75 <-C cc •m TABLE 1 (cont.) Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 36 FeO (wt.%) 0.375 0.75 0.225 0.6875 0.375 0.175 0.375 0.625 0.5625 0.375 0.225 0.5 Total iron (wt.%) 1.5000 3.0000 0.9000 2.7500 1.5000 0.7000 1.5000 2.5000 2.2500 1.5000 0.9000 2.0000 Model redox 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 Cr203 (wt.%) 0.0250 0.0250 0.0250 0.0250 0.0250 0.0210 0.0250 0.0250 0.0250 0.0250 0.0250 0.0250 CoO (wt.%) 0.0220 .0.0220 0.0450 0.0220 0.0220 0,0450 0.0300 0.0220 0.0220 0.0220 0.0400 0.0220 Se (wt.%) 0.0053 0.0027 0.0017 0.0027 0.0046 0.0011 0.0027 0.0027 0.0027 0.0039 0.0017 0.0027 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) 9.74 9.86 .49 .56 .90 .99 11.19 11.33 12.15 12.23 12.42 13.04 TSUV (%) 3.39 1.62 18.98 2.00 4.01 26.80 6.28 2.49 3.11 4.74 19.09 3.91 TSIR (%) .02 1.58 23.31 2.11 .06 .76 .09 2.85 3.88 .10 23.41 .30 TSET (%) 9.54 4.64 19.61 .29 .08 24.75 .84 6.09 7.09 .72 .37 8.36 DW (nm) 579.72 549.97 474.57 550.01 577.57 473.07 487.02 550.02 549.99 574.14 475.74 549.87 Pe {%) 31.58 .12 43.48 13.51 24.63 50.78 9.78 11.87 .21 17.48 37.70 8.51 TABLE 1 (cont.) Ex. 37 Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Ex. 44 Ex. 45 Ex. 46 Ex. 47 Ex. 48 FeO (wt.%) 0.6 0.175 0.375 0.5625 0.375 0.375 0.525 0.375 0.375 0.4375 0.4875 0.375 Total iron (wt.%) 1.500 0.700 1.500 1.500 1.500 1.500 1.500 1.500 1.500 1.750 1.500 1.500 Model redox 0.4000 0.2500 0.2500 0.3750 0.2500 0.2500 0.3500 0.2500 0.2500 0.2500 0.3250 0.2500 Cr203 (wt.%) 0.0250 0.0210 0.0800 0.0250 0.0250 0.0700 0.0250 0.0250 0.0600 0.0250 0.0250 0.0500 CoO (wt.%) 0.0220 0.0400 0.0220 0.0220 0.0250 0.0220 0.0220 0.0220 0.0220 0.0220 0.0220 0.0220 Se (wt.%) 0.0027 0.0011 0.0027 0.0027 0.0027 0.0027 0.0027 0.0032 0.0027 0.0027 0.0027 0.0027 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) 13.10 13.12 13.23 13.40 13.45 • 13.53 13.70 13.78 13.85 14.00 14.02 14.17 ISUV <%) 9.03 26.97 6.09 8.50 6.31 6.13 8.00 .62 6.18 4.96 7.54 6.22 TSIR (%)- . 3.24 .90 .05 3.89 .14 .07 4.69 .14 .09 7.31 .66 .11 TSET (%) / 7.78 .64 .89 8.22 11.61 11.10 8.74 11.50 11.31 .00 9.37 11.54 DW (iron) / 488.02 474.18 554.18 489.76 502.78 553.79 492.18 566.66 553.27 549.62 496.03 552.58 Pe <%) ? 11.44 45.13 12.49 9.38 3.22 11.14 7.32 .21 9.78 6.79 .31 8.43 ' I. t J ^ to TABLE 1 (cont.) Ex. 49 Ex. 50 Ex. 51 Ex. 52 Ex. 53 EX. 54 Ex. 55 Ex. 56 Ex. 57 Ex. 58 Ex. 59 Ex. 60 FeO (wt.%) 0.4500 0.3750 0.4125 0.2250 0.3750 0.3750 0.3750 0.3750 0.3750 0.3750 0.2948 0.3750 Total iron (wt.%) 1.500 1.500 1.500 0.900 1.500 1.500 1.500 1.500 1.500 1.500 1.310 1.500 Model redox 0.3000 0.2500 0.2750 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2250 0.2500 Cr203 (wt.%) 0.0250 0.0400 0.0250 0.0250 0.0300 0.0250 0.0250 0.0250 0.0250 0.0250 0.0280 0.0250 CoO (wt.%) 0.0220 0.0220 0.0220 0.0350 0.0220 0.0220 0.0220 0.0220 0.0220 0.0220 0.0235 0.0220 Se (wt.%) 0.0027 0.0027 0.0027 0.0017 0.0027 0.0027 0.0027 0.0027 0.0027 0.0027 0.0028 0.0027 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.8000 0.7000 0.6000 0.5000 0.4000 0.3000 LTA (%) 14.34 14.51 14.68 14.74 14.86 14.90 14.93 14.95 14.97 14.99 .01 .01 TSUV (%) 7.11 6.27 6.71 19.20 6.31 .44 .58 .72 .87 6.02 7.47 6.18 TSIR (%) 6.86 .14 8.34 23.52 .16 .17 .17 .17 .17 .17 .69 .17 TSET (%) .12 11.77 11.04 21.26 12.02 11.97 12.00 12.03 12.05 12.08 .28 12.11 DW (nm) 503.82 551.62 525.32 477.06 550.13 558.49 557.46 556.28 554.91 553.31 550.91 551.42 Pe (%) 3.46 7.08 2.97 31.54 .72 8.18 7.66 7.14 6.61 6.09 3.66 .57 TABLE 1 (cont.) Ex. 61 Ex. 62 Ex. 63 Ex. 64 Ex. 65 Ex. 66 Ex. 67 Ex. 68 Ex. 69 Ex. 70 Ex. 71 Ex. 72 FeO (wt.%) 0.3750 0.3750 0.3750 0.3493 0.3810 0.3250 0.4960 0.4650 0.3750 0.2600 0.3750 0.2880 Total iron (wt.%) 1.500 1.500 1.500 1.270 1.270 1.300 1.240 1.240 1.500 1.300 1.500 1.280 Model redox 0.2500 0.2500 0.2500 0.2750 0.3000 0.2500 0.4000 0.3750 0.2500 0.2000 0.2500 0.2250 Cr203 (wt.%) 0.0250 0.0250 0.0250 0.0255 0.0260 0.0280 0.0290 0.0260 0.0250 0.0270 0.0250 0.0260 CoO (wt.%) 0.0220 0.0220 0.0220 0.0222 0.0212 0.0226 0.0178 0.0189 0.0220 0.0245 0.0220 0.0240 Se (wt.%) 0.0027 0.0027 0.0027 0.0029 0.0030 0.0029 0.0033 0.0032 0.0027 0.0027 0.0027 0.0027 Ti02 (wt.%) 0.2000 0.2.000 0.2000 0.3000 0.1500 0.2000 0.1000 0.1300 0.0200 0.4800 LTA {%) .04 .04 .04 .04 .05 .05 .05 .06 .06 .07 .08 .08 TSU\T(%) 6.34 6.34 6.34 7.81 8.35 7.82 .25 9.45 6.50 7.10 6.63 6.98 TSIR (%) .17 .17 .17 11.67 9.85 13.30 .43 6.36 .17 19.02 .17 16.29 35ET (%) 12.14 12.14 12.14 13.09 12.09 13.99 9.57 .11 12.17 17.12 12.20 .62 DW (nm) 549.10 549.10 549.10 550.99 550.72 550.89 551.07 550.60 546.28 550.76 543.54 550.58 Pe (%) .04 .04 .04 3.66 3.57 3.69 3.79 3.60 4.53 3.54 4.12 3.82 i tc i i, i TABLE 1 (cont.) Ex. 73 Ex. 74 Ex. 75 Ex. 76 Ex. 77 Ex. 78 Ex. 79 Ex. 80 Ex. 81 Ex. 82 Ex. 83 Ex. 84 FeO (wt.%) 0.4410 0.4375 0.3200 0.3548 0.4688 0.4095 0.4960 0.3840 0.2640 0.4128 0.3750 0.3375 Total iron (wt.%) 1.260 1.250 1.280 1.290 1.250 1.260 1.240 1.280 1.320 1.270 1.500 1.500 Model redox 0.3500 0.3500 0.2500 0.2750 0.3750 0.3250 0.4000 0.3000 0.2000 0.3250 0.2500 0.2250 Cr203 (wt.%) 0.0290 0.0260 0.0260 0.0290 0.0290 0.0260 0.0250 0.0290 0.0280 0.0290 0.0200 0.0250 CoO (wt.%) 0.0193 0.0197 0.0230 0.0217 0.0185 0.0205 0.0182 0.0208 0.0242 0.0200 0.0220 0.0220 Se (wt.%) 0.0032 0.0031 0.0028 0.0029 0.0032 0.0030 0.0032 0.0030 0.0027 0.0031 0.0027 0.0027 Ti02 (wt.%) 0.3000 0.3500 0.3900 0.4400 0.2000 0.2000 LTA (%) .09 .09 .09 .09 .11 .14 .14 .15 .16 .16 .22 .40 TSUV (%) 9.38 8.87 7.42 8.20 9.82 8.34 9.35 8.59 7.18 8.99 6.36 .98 TSIR (%) 7.19 7.33 13.67 11.32 6.24 8.48 .44 9.69 18.60 8.33 .18 12.44 TSET (%) .59 .66 14.20 12.91 .05 11.32 9.58 12.02 16.92 11.26 12.27 13.49 DW (nm) 550.53 550.77 550.65 550.53 550.80 550.87 550.70 551.11 550.86 550.82 547.74 559.28 Pe (%) 3.77 3.79 3.76 3.79 3.80 3.95 3.93 3.89 3.70 3.85 4.37 7.45 TABLE 1 (cont.) Ex. 85 Ex. 86 Ex. 87 Ex. 88 Ex. 89 Ex. 90 Ex. 91 Ex. 92 Ex. 93 Ex. 94 Ex. 95 Ex. 96 FeO (wt.%) 0.3750 0.3750 0.1750 0.3000 0.3750 0.3750 0.3750 0.2250 0.3120 0.2990 0.2860 0.2990 Total iron (wt.%) 1.500 1.500 0.700 1.500 1.500 1.500 1.500 0.900 1.200 1.150 1.100 1.100 Model redox 0.2500 0.2500 0.2500 0.2000 0.2500 0.2500 0.2500 0.2500 0.2600 0.2600 0.2600 0.2720 Cr203 (wt.%) 0.0250 0.0100 0.0210 0.0250 0.0005 0.0250 0.0250 0.0250 0.0230 0.0280 0.0320 0.0320 CoO (wt.%) 0.0220 0.0220 0.0350 0.0220 0.0220 0.0200 0.0220 0.0300 0.0196 0.0200 0.0201 0.0198 STIyvt.%) 0.0025 0.0027 0.0011 0.0027 0.0027 0.0027 0.0020 0.0017 0.0025 0.0024 0.0025 0.0025 rnoi (wt.%) 0.2000 . 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.0280 0.0280 0.0280 0.0280 lta|(%) .58 .59 .72 .78 .95 16.20 17.04 17.54 18.03 18.05 18.02 18.06 TSUV (%) 6.65 6.40 27.14 .65 6.45 6.35 7.50 19.31 9.55 .19 .64 .87 TSIF (%) .18 .21 31.05 .27 .23 .19 .22 23.63 11.9 12.88 13.95 12.88 TSE" (%) 12.43 12.54 26.69 .14 12.80 12.53 13.22 22.30 .38 .96 16.53 .95 PW (nm) 528.36 543.24 475.35 564.59 533.25 560.22 496.92 478.60 556.5 547.3 549.7 545.6 f?e (<3 r 3.26 3.03 39.04 9.88 1.81 8.39 .84 .04 4.43 3.36 3.62 3.27 • •-is- TABLE 1 (cont.) Ex. 97 Ex. 98 Ex. 99 Ex. 100 Ex. 101 Ex. 102 Ex. 103 Ex. 104 Ex. 106 Ex. 106 Ex. 107 Ex. 108 FeO (wt.%) 0.3750 0.1750 0.2250 0.3750 0.2250 0.2250 0.3750 0.1750 0.1750 0.2250 0.3750 0.1750 Total iron (wt.%) 1.500 0.700 0.900 1.500 0.900 0.900 1.500 0.700 0.700 0.900 1.500 0.700 Model redox 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 Cr203 (wt.%) 0.0250 0.0210 0.0250 0.0250 0.0250 0.0250 0.0250 0.0210 0.0210 0.0250 0.0250 0.0210 CoO (wt.%) 0.0220 0.0300 0.0107 0.0150 0.0250 0.0107 0.0220 0.0070 0.0250 0.0107 0.0100 0.0070 Se (wt.%) 0.0015 0.0011 0.0060 0.0027 0.0017 0.0053 0.0008 0.0060 0.0011 0.0046 0.0027 0.0053 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) 18.68 18.88 19.28 19.57 .92 21.12 21.31 21.65 22.73 23.19 23.68 23.86 TSUV (%) 8.46 27.31 7.87 6.39 19.42 9.14 .02 9.26 27.48 .62 6.42 .85 TSIR (%) .25 31.19 23.35 .25 23.73 23.46 .29 31.12 31.34 23.57 .30 31.22 TSET (%) 14.13 27.91 .49 13.63 23.52 21.34 .65 .68 29.35 22.31 14.95 26.65 DW (nm) 491.19 476.64 583.88 568.92 480.62 582.85 487.95 585.96 478.18 581.60 572.24 585.04 Pe (%) .53 32.49 41.80 16.72 18.24 36.18 17,10 49.85 .55 .33 24.81 44.03 TABLE 1 (cont.) Ex. 109 Ex. 110 Ex. 111 Ex. 112 Ex. 113 Ex. 114 Ex. 115 Ex. 116 Ex. 117 Ex. 118 Ex. 119 EX. 120 FeO (wt.%) 0.2250 0.2060 0.3185 0.2970 0.3600 0.2750 0.3263 0.3440 0.3395 0.2585 0.2925 0.2040 Total iron (wt.%) 0.900 1.030 0.980 0.990 0.960 1.000 0.870 0.860 0.970 0.940 0.900 1.020 Model redox 0.2500 0.2000 0.3250 0.3000 0.3750 0.2750 0.3750 0.4000 0.3500 0.2750 0.3250 0.2000 Cr203 (wt.%) 0.0250 0.0240 0.0240 0.0240 0.0250 0.0240 0.0270 0.0280 0.0240 0.0250 0.0260 0.0235 CoO (wt.%) 0.0200 0.0170 0.0138 0.0144 0.0126 0.0150 0.0135 0.0131 0.0132 0.0155 0.0145 0.0172 Selyvt.%) 0.0017 0.0018 0.0022 0.0021 0.0023 0.0020 0.0022 0.0022 0.0022 0.0020 0.0021 0.0018 TiO^ (wt.%) 0.2000 0.3000 0.4700 0.2600 0.3100 0.2600 LTAj(%) .01 .01 .04 .06 .07 .08 .08 .08 .08 .08 .09 .09 TSU,V (%) 19.53 12.23 14.95 14.39 16.20 13.84 16.42 16.44 .57 13.87 .07 11.78 TSIR (%) 23.84 26.16 13.98 .73 11.18 17.75 13.41 12.18 12.48 19.46 16.12 26.47 TSET (%) 24.95 .29 18.67 19.63 17.11 .75 18.38 17.65 17.85 21.69 19.87 .45 DW (nm) 483.91 650.56 551.23 551.01 550.87 551.07 550.51 550.63 550.78 550.87 550.95 550.70 Pe (j%) 11.21 3.69 3.72 3.71 3.75 3.75 3.55 3.88 3.65 3.67 3.65 3.94 TABLE 1 (cont.) Ex. 121 Ex. 122 Ex. 123 Ex. 124 Ex. 125 Ex. 126 Ex. 127 Ex. 128 Ex. 129 Ex. 130 Ex. 131 Ex. 132 FeO (wt.%) 0.2183 0.2400 0.3800 0.2525 0.3115 0.2295 0.2760 0.2250 0.1750 0.1750 0.2250 0.4250 Total iron (wt.%) 0.970 0.960 0.950 1.010 0.890 1.020 0.920 0.900 0.700 0.700 0.900 1.700 Model redox 0.2250 0.2500 0.4000 0.2500 0.3500 0.2250 0.3000 0.2500 0.2500 0.2500 0.2500 0.2500 Cr203 (wt.%) 0.0230 0.0240 0.0250 0.0240 0.0270 0.0240 0.0250 0.0250 0.0210 0.0210 0.0250 0,0250 CoO (wt.%) 0.0167 0.0162 0.0120 0.0156 0.0140 0.0162 0.0150 0.0107 0.0070 0.0200 0.0107 0.0107 Se (wt.%) 0.0019 0.0019 0.0023 0.0020 0.0021 0.0019 0.0020 0.0039 0.0046 0.0011 0.0032 0.0017 Ti02 (wt.%) 0.2300 0.4200 0.4500 0.4300 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) .09 .10 .13 .15 .17 .19 .27 .52 26.35 27.45 28.15 28.38 TSUV (%) 12.79 12.80 16.85 13.34 .24 12.83 14.09 12.33 12.71 27.65 14.33 9.99 TSIR (%) 24.41 21.59 .06 .12 14.53 22.90 17.66 23.68 31.33 31.49 23.80 8.20 TSET (%) 24.40 22.83 16.50 22.08 18.99 23.60 .77 23.44 27.77 31.06 24.75 16.22 DW (nm) 550.83 550.53 551.00 550.49 550.57 551.12 550.65 579.95 584.02 480.17 577.51 545.94 Pe (%} 3.51 3.84 3.74 3.71 3.91 3.80 3.82 24.29 37.88 18.25 18.11 7.52 TABLE 1 (cont.) Ex, 133 Ex. 134 Ex. 135 Ex. 136 Ex. 137 Ex. 138 Ex 139 Ex. 140 Ex. 141 Ex. 142 Ex. 143 Ex. 144 FeO (wt.%) 0.3750 0.4000 0.1750 0.3750 0.2250 0.3500 0 .250 0.2250 0.2250 0.3250 0.3600 0.2250 Total iron (wt.%) 1.500 1.600 0.700 1.500 0.900 1.400 0.900 0.900 0.900 1.300 0.900 0.900 Model redox 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.4000 0.2500 Cr203 (wt.%) 0.0250 0.0250 0.0210 0.0250 0.0250 0.0250 0.0800 0.0250 0.0700 0.0250 0.0250 0.0600 CoO (wt.%) 0.0050 0.0107 0.0070 0.0107 0.0150 0.0107 0.0107 0.0107 0.0107 0.0107 Q.0107 0.0107 Se (wt.%) 0.0027 0.0017 0.0039 0.0017 0.0017 0.0017 0.0017 0.0025 0.0017 0.0017 0.0017 0.0017 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 t-TA <%) 28.72 29.13 29.19 29.91 29.96 .71 .71 31.14 31.44 31.53 32.11 32.20 T$UV (%) 6.46 .84 14.90 11.76 19.65 12.78 19.13 16.64 19.24 13.90 23.95 19.35 TSIR (%) .35 9.34 31.44 .65 23.95 12.15 23.80 23.91 23.84 13.89 11.55 23.89 TSET (%) 16.56 17.23 29.09 18.35 26.65 19.59 .48 26.29 .96 .97 .75 26.46 PVV (nm) 574.22 546.65 582.80 547.43 492.96 548.31 556.15 573.03 556.08 549.30 492.90 555.97 Pe (%) 32.55 7.16 31.42 6.80 4.27 6.44 11.87 11.83 .56 6.07 .63 9.24 TABLE 1 (cont.) Ex. 145 Ex. 146 Ex. 147 Ex. 148 Ex. 149 Ex. 150 Ex. 151 Ex. 152 Ex. 153 Ex. 154 Ex. 155 Ex. 156 FeO (wt.%) 0.3000 0.1750 0.3375 0.2250 0.3150 0.1750 0.2750 0.2250 0.2925 0.2250 0.2700 0.2500 Total iron (wt.%) 1.200 0.700 0.900 0.900 0.900 0.700 1.100 0.900 0.900 0.900 0.900 1.000 Model redox 0.2500 0.2500 0.3750 0.2500 0.3500 0.2500 0.2500 0.2500 0.3250 0.2500 0.3000 0.2500 Cr203 (wt.%) 0.0250 0.0210 0.0250 0.0500 0.0250 0.0210 0.0250 0.0250 0.0250 0.0400 0.0250 0.0250 CoO (wt.%) 0.0107 0.0070 0.0107 0.0107 0.0107 0.0150 • 0.0107 0.0107 0.0107 0.0107 0.0107 0.0107 Se (wt.%) 0.0017 0.0032 0.0017 0.0017 0.0017 0.0011 0.0017 0.0020 0.0017 0.0017 0.0017 0.0017 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) 32.37 32.44 32.57 32.99 33.05 33.22 33.24 33.52 33.54 33.80 34.03 34.14 TSUV (%) .15 17.46 23.17 19.46 22.43 27.83 16.52 18.52 21.72 19.57 21.03 18.05 TSIR (%) .90 31.55 13.01 23.33 14.68 31.64 . 18.23 24.00 16.58 23.98 18.74 .92 TSET (%) 22.52 .63 21.68 26.98 22.72 33.10 24.24 27.54 23.89 27.52 .21 26.19 DW (nm) 550.42 581.19 495.48 555.80 499.55 483.52 551.73 565.70 507.34 555.55 524.51 553.17 Pe (%) .71 24.72 4.48 7.93 3.37 .68 .36 7.33 2.42 6.61 2.27 .00 f TABLE 1 (cont.) ro Ex. 157 Ex. 158 Ex. 159 Ex. 160 Ex. 161 Ex. 162 Ex. 163 Ex. 164 Ex. 165 Ex. 166 Ex. 167 Ex. 168 FeO (wt.%) 0.2475 0.2250 0.2250 0.2250 0.2250 0.2250 0.2250 0.2250 0.3038 0.2050 0.1760 0.1680 Total iron (wt.%) 0.900 0.900 0.900 0.900 0.900 0.900 0.900 0.900 0.810 0.820 0.880 0.840 Model redox 0.2750 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.3750 0.2500 0.2000 0.2000 Cr203 (wt.%) 0.0250 0.0300 0.0250 0.0250 0.0250 0.0250 0.0250 0.0250 0.0270 0.0250 0.0280 0.0270 CoQ (wt.%) 0.0107 0.0107 0.0107 0.0107 0.0107 0.0107 0.0107 0.0107 0.0084 0.0113 0.0119 0.0122 Se-tWt.%) 0.0017 0.0017 0.0017 0.0017 0.0017 0.0017 0.0017 0.0017 0.0020 0.0017 0.0016 0.0016 Ti02 (wt.%) 0.2000 0.2000 0.8000 0.7000 0.6000 0.5000 0.4000 0.3000 0.2200 0.1500 LTA (%) 34.54 34.63 34.75 34.80 34.85 34.91 34.96 .01 .02 .03 .05 .05 TSUV <%) .38 19.69 16.79 17.24 17.72 18.20 18.70 19.22 24.83 21.12 .29 .31 TSIR (%) 21.22 24.03 24.05 24.05 24.05 24.05 24.05 24.05 .60 26.90 31.69 33.17 TSET (%) 26.70 28.08 27.94 28.01 28.08 28.15 28.23 28.30 23.83 .05 32.59 33.42 DW (nm) 544.21 555.15 562.59 561.76 560.81 559.69 558.39 556.81 550.61 550.96 550.65 550.80 Pe (%) 3.34 .30 7.81 7.28 6.76 6.23 .70 .17 3.72 3.47 3.73 3.55 04 IV) 00 ro hO r\a TABLE 1 (cont.) Ex. 169 Ex. 170 Ex. 171 Ex. 172 Ex. 173 Ex. 174 Ex. 175 Ex. 176 Ex. 177 Ex. 178 Ex. 179 Ex. 180 FeO (wt.%) 0.2250 0.2250 0.2250 0.1868 0.2730 0.2550 0.2150 0.2365 0.3200 0.2250 0.2870 0.1958 Total iron (wt.%) 0.900 0.900 0.900 0.830 0.840 0.850 0.860 0.860 0.800 0.900 0.820 0.870 Model redox 0.2500 0.2500 0.2500 0.2250 0.3250 0.3000 0.2500 0.2750 0.4000 0.2500 0.3500 0.2250 Cr203 (wt.%) 0.0250 0.0250 0.0250 0.0270 0.0280 0.0280 0.0280 0.0280 0.0270 0.0250 0.0270 0.0280 CoO (wt.%) 0.0107 0.0107 0.0107 0.0118 0.0092 0.0097 0.0108 0.0102 0.0079 0.0107 0.0088 0.0113 Se (wt.%) 0.0017 0.0017 0.0017 0.0016 0.0019 0.0018 0.0017 0.0018 0.0020 0.0017 0.0019 0.0017 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.3200 0.1000 LTA (%) .06 .06 .06 .08 .09 .09 .10 .11 .11 .11 .12 .13 TSUV (%) 19.75 19.75 19.75 .17 23.31 22.65 21.54 21.99 .59 .29 24.15 .91 TSIR (%) 24.05 24.05 24.05 29.82 18.43 .35 .42 22.54 14.29 24.05 17.08 28.33 TSET (%) 28.37 28.37 28.37 31.58 .39 26.45 29.23 27.65 23.15 28.45 24.69 .81 DW (nm) 554.86 554.86 554.86 550.80 550.76 550.70 550.37 550.89 550.75 552.42 551.11 550.97 Pe (%) 4.64 4.64 4.64 3.81 3.93 3.91 3.76 3.92 3.76 • 4.11 3.79 3.81 TABLE 1 (cont.) Ex. 181 Ex. 182 Ex. 183 Ex. 184 Ex. 185 Ex. 186 Ex. 187 Ex. 188 Ex. 189 Ex. 190 Ex. 192 Ex. 192 FeO (wt.%) 0.2228 0.2250 0.2730 0.2568 0.2888 0.2430 0.3040 0.2250 0.2025 0.2250 0.1800 0.2250 Total iron (wt.%) 0.810 0.900 0.780 0.790 0.770 0.810 0.760 0.900 0.900 0.900 0.900 0.900 Model redox 0.2750 0.2500 0.3500 0.3250 0.3750 0.3000 0.4000 0.2500 0.2250 0.2500 0.2000 0.2500 Cr203 (wt.%) 0.0260 0.0250 0.0260 0.0265 0.0260 0.0250 0.0255 0.0200 0.0250 0.0250 0.0250 0.0250 CoO (wt.%) 0.0108 0.0107 0.0095 0.0098 0.0089 0.0104 0.0086 0.0107 0.0107 0.0100 0.0107 0.0107 Se (wt.%) 0.0017 0.0017 0.0018 0.0018 0.0019 0.0017 0.0019 0.0017 0.0017 0.0017 0.0017 0.0015 Ti02 (wt.%) 0.3200 0.0200 0.4600 0.2900 0.2700 0.4900 0.4200 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) .15 .15 .16 .17 .18 .20 .21 .50 .59 .97 36.14 36.14 TSUV (%) 21.34 .74 22.52 22.73 24.12 .99 24.01 19.80 19.14 19.76 18.55 .61 TSIR (%) 24.35 24.05 18.45 .16 16.93 21.77 .59 24.07 27.29 24.06 31.00 24.08 TSET (%) 28.67 28.51 .41 26.39 24.63 27.24 23.87 28.67 .27 28.68 32.42 28.96 DW (nm) 550.59 549.96 550.81 550.78 550.91 550.73 550.79 554.47 560.86 559.34 564.72 537.17 Pe (%) 3.72 3.69 3.98 3.79 3.73 3.96 3.87 3.99 .98 .81 7.33 2.96 17 - « TABLE 1 (cont.) Ex. 193 Ex. 194 Ex. 195 Ex. 196 Ex. 197 Ex. 198 Ex. 199 Ex. 200 Ex. 201 Ex. 202 Ex. 203 Ex. 204 FeO (wt.%) 0.1750 0.2250 0.2250 0.3500 0.3250 0.1750 0.1750 0.3000 0.1750 0.2250 0.1750 0.2750 Total iron (wt.%) 0.700 0.900 0.900 1.400 1.300 0.700 0.700 1.200 0.700 0.900 0.700 1.100 Model redox 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500 Cr203 (wt.%) 0.0210 0.0100 0.0005 0.0210 0.0210 0.0210 0.0800 0.0210 0.0700 0.0250 0.0210 0.0210 CoO (wt.%) 0.0070 0.0107 0.0107 0.0070 0.0070 0.0070 0.0070 0.0070 0.0070 0.0107 0.0100 0.0070 Se (wt.%) 0.0025 0.0017 0.0017 0.0011 0.0011 0.0020 0.0011 0.0011 0.0011 0.0008 0.0011 0.0011 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) 36.15 36.39 37.27 37.74 38.74 39.14 39.29 39.76 40.23 40.24 40.32 40.81 TSUV (%) .46 19.92 .03 .66 16.96 22.92 27.23 18.38 27.37 23.94 28.00 19.95 TSIR (%) 31.66 24.12 24.16 12.05 13.79 31.74 31.55 .80 31.61 24.20 31.79 18.13 TSET (%) 32.46 29.28 29.89 22.48 23.95 33.97 33.23 .58 33.85 31.25 .55 27.40 DW (nm) 578.76 553.07 549.31 541.05 542.27 575.77 555.78 543.64 555.68 494.01 494.99 545.18 Pe (%) 17.83 2.68 1.44 .63 .36 12.83 11.51 .09 .21 6.17 3.20 4.83 ro i TABLE 1 (cont.) - - Ex. 205 Ex. 206 Ex. 207 Ex. 208 Ex. 209 Ex. 210 Ex. 211 Ex. 212 Ex. 213 Ex. 214 Ex. 215 Ex. 216 -FeO (wt.%) 0.1750 0.2500 0.1750 0.2800 0.1750 0.2625 0.2250 0.2450 0.1750 0.2250 0.2275 0.2000 IJPptal irbn (wt.%) 0.700 1.000 0.700 0.700 0.700 0.700 0.900 0.700 0.700 0.900 0,700 0.800 Model redox 0.2500 0.2500 0.2500 0.4000 0.2500 0.3750 0.2500 0.3500 0.2500 0.2500 0.3250 0.2500 Cr203 jwt.%) 0.0600 0.0210 0.0500 0.0210 0.0210 0.0210 0.0210 0.0210 0.0400 0.0250 0.0210 0.0210 CoO (wt.%) 0.0070 0.0070 0.0070 0.0070 0.0070 0.0070 0.0070 0.0070 0.0070 0.0050 0.0070 0.0070 Se (wt.%) 0.0011 0.0011 0.0011 0.0011 0.0015 0.0011 0.0011 0.0011 0.0011 0.0017 0.0011 0.0011 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 0.2000 LTA (%) 41.21 41.90 42.22 42.25 42.45 42.74 43.01 43.24 43.27 43.29 43.76 44.16 TSUV (%) 27.52 21.68 27.67 32.61 .67 31.79 23.59 31.01 27.82 19.88 .25 .73 TSIR (%) 31.66 .83 31.72 17.65 31.82 19.44 23.97 21.44 31.78 24.18 23.65 27.63 TSET (%) 34.49 29.44 .15 28.68 .70 29.79 31.73 31.01 .85 31.10 32.35 34.32 DW (nm) 555.53 546.93 555.32 494.20 569.54 496.90 548.91 501.21 555.00 570.22 509.20 551.16 Pe (%) 8.90 4.57 7.59 4.43 7.81 3.54 4.31 2.70 6.29 14.10 2.01 4.06 ro CD M ro po TABLE 1 (cont.) Ex. 217 Ex. 218 Ex. 219 Ex. 220 Ex. 221 Ex. 222 Ex. 223 Ex. 224 Ex. 225 Ex. 226 Ex. 227 Ex. 228 FeO (wt.%) 0.2100 0.1750 0.1925 0.1750 0.1750 0.2210 0.1440 0.2600 0.2380 0.2100 0.2345 0.1460 Total iron (wt.%) 0.700 0.700 0.700 0.700 0.700 0.680 0.720 0.650 0.680 0.700 0.670 0.730 Model redox 0.3000 0.2500 0.2750 0.2500 0.2500 0.3250 0.2000 0.4000 0.3500 0.3000 0.3500 0.2000 Cr203 (wt.%) 0.0210 0.0300 0.0210 0.0210 0.0210 0.0210 0.0240 0.0250 0.0250 0.0255 0.0215 0.0245 CoO (wt.%) 0.0070 0.0070 0.0070 0.0070 0.0070 0.0060 0.0079 0.0047 0.0053 0.0060 0.0057 0.0077 Se (wt.%) 0.0011 0.0011 0.0011 0.0011 0.0011 0.0012 0.0010 0.0013 0.0013 0.0012 0.0012 0.0010 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.8000 0.7000 0.2000 0.2000 0.3000 LTA (%) 44.28 44.35 44.81 44.95 45.01 45.03 45.04 45.05 45.06 45.07 45.07 45.07 TSUV (%) 29.51 27.97 28.80 23.80 24.47 .09 26.82 34.11 32.22 .62 .22 27.82 TSIR (%) 26.11 31.83 28.84 31.89 31.89 24.54 38.12 19.73 22.30 26.10 22.75 37.68 TSET (%) 33.83 36.57 .46 36.68 36.77 33.15 40.43 .51 31.90 33.96 32.14 40.25 DW (nm) 525.66 554.49 543.44 562.94 562.02 550.93 551.27 550.47 550.26 550.86 550.56 550.90 Pe (%) 2.00 4.99 2.82 6.99 6.46 3.55 3.78 3.71 3.76 3.87 3.72 3.59 ^ ! TABLE 1 (cont.) £ Ex. 229 Ex. 230 Ex. 231 Ex. 232 Ex. 233 Ex. 234 Ex. 235 Ex. 236 Ex. 237 Ex. 238 Ex. 239 Ex. 240 EeO (wt.%) 0.1953 0.1750 0.1725 0.2513 0.1800 0.1750 0.2243 0.1643 0.1750 0.2475 0.2560 0.1750 <!§)tal iron (wt.%) 0.710 .0.700 0.690 0.670 0.720 0.700 0.690 0.730 0.700 0.660 0.640 0.700 Model redox 0.2750 0.2500 0.2500 0.3750 0.2500 0.2500 0.3250 0.2250 0.2500 0.3750 0.4000 0.2500 Cr203 (wt.%) 0.0255 0.0210 0.0230 0.0255 0.0245 0.0210 0.0255 0.0245 0.0210 0.0210 0.0215 0.0210 CoO (wt.%) 0.0064 0.0070 0.0070 0.0049 0.0068 0.0070 0.0056 0.0072 0.0070 0.0054 0.0052 0.0070 Se (wt.%) 0.0011 0.0011 0.0011 0.0013 0.0011 0.0011 0.0012 0.0011 0.0011 0.0012 0.0012 0.0011 Ti02 (wt.%) 0.6000 0.1500 0.5000 0.4000 0.4200 0.5200 0.3000 LTA (%) 45.07 45.08 45.10 45.12 45.13 45.15 45.15 45.17 45.21 45.22 45.27 45.28 TSUV (%) 29.87 .16 28.73 33.06 29.08 .86 31.45 28.35 26.59 .17 .49 27.34 TSIR (%) 28.38 31.89 32.33 .71 .96 31.89 24.08 33.90 31.89 21.16 .19 31.89 TSET (%) .20 36.86 37.40 31.04 36.65 36.96 32.90 38.24 37.05 31.29 .75 37.15 DW (nm) 550.41 560.95 551.62 550.70 550.88 559.66 550.68 550.94 558.12 550.89 550.76 556.18 Pe (%) . 3.79 .93 3.61 3.88 3.72 .40 3.87 3.71 4.87 3.90 4.01 4.35 • t • • TABLE 1 (cont.) Ex. 241 Ex. 242 Ex. 243 Ex. 244 Ex. 245 Ex. 246 Ex. 247 Ex. 248 Ex. 249 Ex. 250 Ex. 251 Ex. 252 FeO (wt.%) 0.1925 0.2070 0.1750 0.1750 0.1750 0.1620 0.1750 0.1750 0.1750 0.1575 0.1400 0.1500 Total iron (wt.%) 0.700 0.690 0.700 0.700 0.700 0.720 0.700 0.700 0.700 0.700 0.700 0.600 Model redox 0.2750 0.3000 0.2500 0.2500 0.2500 0.2250 0.2500 0.2500 0.2500 0.2250 0.2000 0.2500 Cr203 (wt.%) 0.0230 0.0210 0.0210 0.0210 0.0210 0.0220 0.0210 0.0200 0.0210 0.0210 0.0210 0.0210 CoO (wt.%) 0.0066 0.0064 0.0070 0.0070 0.0070. 0.0075 0.0070 0.0070 0.0070 0.0070 0.0070 0.0070 Se (wt.%) 0.0011 0.0011 0.0011 0.0011 0.0011 0.0010 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 Ti02 (wt.%) 0.2000 0.3800 0.2000 0.2000 0.2000 0.3000 0.1000 0.2000 0.0200 0.2000 0.2000 0.2000 LTA (%) 45.29 45.35 45.35 45.35 45.35 45.35 45.42 45.46 45.47 45.90 46.46 46.57 TSUV (%) 28.78 28.32 28.11 28.11 28.11 26.77 28.90 28.12 29.56 27.44 26.79 .79 TSIR (%) 28.84 26.57 31.89 31.89 31.89 34.36 31.89 31.89 31.89 .28 39.06 36.86 TSET (%) .54 34.31 37.25 37.25 37.25 38.55 37.35 37.33 37.43 39.23 41.41 40.58 DW (nm) 550.70 550.64 553.71 553.71 553.71 550.30 550.44 553.59 546.98 559.73 563.70 556.63 Ee-W, 3.77 3.80 3.82 3.82 3.82 3.71 3.29 3.69 2.87 4.84 .88 3.57 ■ • J ? 1 ■' i TABLE 1 (cont.) ! < < i i I \ ro oo ro ro Ex. 253 Ex. 254 Ex. 255 Ex. 256 jj^O (wt.%) 0.1750 0.1750 0.1750 0.1750 Total iron (wt.%) 0.700 0.700 0.700 0.700 Model redox 0.2500 0.2500 0.2500 0.2500 -Cf2Q3fwt.%) 0.0100 0.0210 0.0005 0.0210 CoO (wt.%) 0.0070 0.0070 0.0070 0.0050 Se (wt.%) 0.0011 0.0008 0.0011 0.0011 Ti02 (wt.%) 0.2000 0.2000 0.2000 0.2000 LTA {%) 46.61 47.69 47.75 49.07 TSUV i%) 28.28 .09 28.43 28.18 TSIR (%) 31.95 31.93 32.01 31.95 TSET (%) 38.11 38.53 38.89 38.50 DW (nm) 551.69 509.82 545.77 565.18 Pe (%} 2.39 2.14 1.16 7.39 - TABLE 2 Ex. 257 Ex. 258 Ex. 259 Ex. 260 Ex. 261 Ex. 262 Ex. 263 Ex. 264 Ex. 265 FeO (wt.%) 0.3232 0.2980 0.3080 0.2980 0.3500 0.2890 0.3500 0.3500 0.3080 Total iron (wt.%) 1.103 1.103 1.100 1.103 1.083 1.070 1.083 1.083 1.100 Model redox 0.2929 0.2702 0.2800 0.2702 0.3232 0.2701 0.3232 0.3232 0.2800 Cr203 (wt.%) 0.0302 0.0302 0.0302 0.0302 0.0293 0.0302 0.0293 0.0293 0.0302 CoO (wt.%) 0.0128 0.0125 0.0128 0.0119 0.0110 0.0119 0.0100 0.0090 0.0100 Se (wt.%) 0.0010 0.0010 0.0010 0.0009 0.0010 0.0009 0.0010 0.0010 0.0010 Ti02 (wt.%) 0.1940 0.1940 0.1940 0.1940 0.3510 0.1940 0.3510 0.3510 0.1940 LTA (%) 31.13 31.95 32.59 33.18 33.47 33.52 34.63 .84 .87 TSUV (%) 16.53 .93 .62 16.28 19.74 16.79 19.76 19.78 .69 TSIR (%) 12.31 14.26 13.45 14.27 .54 .05 .54 .55 13.47 TSET (%) 21.38 22.72 22.93 23.23 21.37 23.84 21.74 22.12 23.98 DW (nm) 497.4 502.2 433.5 502.5 497.8 502.1 502.2 509.2 505.2 6.57 .03 6.86 .14 .59 .1 4.52 3.69 3.75 TABLE 3 r~ Ex. 266 Ex. 267 Ex. 268 Ex. 269 F|8 (wt.%) 0.3060 0.3080 0.3400 0.3500 T6T&I iron (wt.%) 1.099 1.103 1.101 1.110 Redox 0.2790 0.2800 0.3100 0.3160 Cr203 (wt.%) 0.0286 0.0302 0.0288 0.0323 CoO (wt.%) 0.0128 0.0128 0.0129 0.0129 Se (wt.%) 0.0012 0.0010 0.0008 0.0007 Ti02 (wt.%) 0.3550 0.1940 0.3500 0.1940 LTA (%) 28.33 29.47 29.91 .25 TSUV (%) 14.14 .72 16.28 19.16 TSIR (%) 12.99 12.72 .44 9.31 TSET (%) 19.56 .12 19.13 18.93 DW (nm) 509.2 497.2 494.2 491.1 Pe (%) 4.06 .59 8.89 11.88 CM ro oo ro ro ro 328 2 1 1 21 Referring to Tables 1, 2 and 3, the present invention provides a green colored glass using a standard soda-lime-silica glass base composition and additionally iron, cobalt, selenium and chromium, and optionally titanium, as infrared and ultraviolet radiation absorbing 5 materials and colorants. As may be seen, not all of the examples are the same color, as indicated by the dominant wavelength (DW) and excitation purity (Pe). In the present invention, it is preferred that the glass have a color characterized by a dominant wavelength in the range of about 480 to 565 nanometers, preferably about 495 to 560 10 nanometers, with an excitation purity of no higher than about 20%,. preferably no higher than about 10%, and more preferably no higher than about 7%. It is anticipated that the color of the glass may vary within this dominant wavelength range to provide a desired product. For example, a green blue glass may be produced at a dominant wavelength 15 of about 485 to 515 nanometers, preferably about 490 to 510 nanometers, with an excitation purity of no higher than 10%, preferably not higher than 7%, while a green yellow glass may be produced at a dominant wavelength of about 535 to 565 nanometers, preferably about 540 to 560 nanometers, with an excitation purity of no higher than 20 10%, preferably not higher than 5%.

The green colored, infrared and ultraviolet radiation absorbing glasses disclosed in the present invention have a luminous transmittance (LTA) of up to 60 percent. In one particular embodiment, the glasses include about 0.6 to 4 wt.% total iron, about 0.13 to 0.9 wt.% FeO, 25 about 40 to 500 PPM CoO, about 5 to 70 PPM Se, about 15 to 800 PPM Cr203 and 0.02 to about 1 wt.% TiOz. In another embodiment, the glasses include about 1 to less than 1.4 wt.% total iron, about 0.2 to 0.60 wt.% FeO, greater than 200 to about 500 PPM CoO, aboutJ5 to 70 PPM Se, greater than 200 to about 800 PPM Cr203 and 0 to about \ 328 2 2 2 1 wt.% Ti02. The redox ratio for these glasses is maintained between about 0.20 to 0.40, preferably between about 0.22 to 0.35, more preferably between about 0.23 to 0.28. These glass compositions also have a TSUV of no greater than about 40%, preferably no greater than 5 about 35%, a TSIR of no greater than about 45%, preferably no greater than about 40%, and a TSET of no greater than about 50%, preferably no greater than about 45%.

The glass compositions of the present invention may be provided with varying levels of spectral performance, depending on the particular 10 application and desired luminous transmittance. In one embodiment of the invention, for a green colored, infrared and ultraviolet radiation absorbing glass having an LTA of less than 20% at at least one thickness in the range of 1.8 to 5.0 mm, the glass composition includes about 1 to less than 1.4 wt.% total iron; about 0.22 to 0.5 wt.% FeO, 15 preferably about 0.3 to 0.5 wt.%; greater than 200 to about 450 PPM CoO, preferably greater than 200 to about 350 PPM; about 10 to 60 PPM Se, preferably about 35 to 50 PPM; about 250 to 400 PPM Cr203, preferably about 250 to 350 PPM; and 0 to about 1 wt.% Ti02, preferably about 0.02 to 0.5 wt.%. The glass compositions within this 20 luminous transmittance range have a TSUV of no greater than about 30%, preferably no greater than 12%, a TSIR of no greater than about 35%, preferably no greater than about 20%, and a TSET of no greater than about 30%, preferably no greater than about 20%.

In another embodiment of the invention, for a green colored, 25 infrared and ultraviolet radiation absorbing glass having an LTA of less than 20 to 60% s* at least one thickness in the range of 1.8 to 5.0 mm, the glass composition includes about 1 to less than 1.4 wt.% total iron; about 0.25 to 0.4 wt.% FeO; greater than 200 to about 250 PPM CoO; ;about 10 to 30 PPM Se; greater than 200 to about 250 PPMrCr^C^; ;^ $97 ;328 2 2 2 ;23 - ;and about 0.02 to 0.5 wt.% Ti02. ;The glass compositions within this luminous transmittance range have a TSUV of no greater than about 35%, preferably no greater than 20%, a TSIR of no greater than about 40%, preferably no greater than about 5 15%, iand a TSET of no greater than about 45%, preferably, no greater than about 25%. ;In another embodiment of the invention, for a green colored, ;infrared and ultraviolet radiation absorbing glass having an LTA of 20 to 60% at a reference thickness of 4.06 mm, the glass composition 10 includes greater than 0.7 to about 2 wt.% total iron, preferably about 0.8 to 1.5 wt.%; about 0.13 to 0.6 wt.% FeO, preferably about 0.14 to 0.43 wt.%; greater than 200 to about 300 PPM CoO, preferably greater than 200 to about 250 PPM; about 5 to 70 PPM Se, preferably about 8 to 60 PPM; greater than 200 to about 300 PPM Cr203, preferably 15 greater than 200 to about 250 PPM; and 0 to about 1 wt.% Ti02, ;preferably about 0.02 to 0.5 wt.%. The glass compositions within this luminous transmittance range have a TSUV of no greater than about 35%, a TSIR of no greater than about 40%, and a TSET of no greater than about 45%. ;20 In another embodiment of the invention, the green colored, ;infrared and ultraviolet radiation absorbing glass composition includes 0.9 to 1.3 wt.% total iron, preferably 1.083 to 1.11 wt.%; 0.25 to 0.40 wt.% FeO, preferably 0.306 to 0.35 wt.%; 80 to 130 PPM CoO, ;preferably 90 to 128 PPM; 8 to 15 PPM Se, preferably 10 to 12 PPM; 25 250 to 350 PPM Cr203, preferably 286 to 302 PPM; and 0.1 to 0.5 wt.% Ti02, preferably 0.194 to 0.355 wt.%. These glasses have a luminous transmittance (LTA) of 25 to 40 percent, a total solar ultraviolet transmittance (TSUV) of about 7.5 percent or less, a tibial solar ;1397 ;2 - ;V ;328222 ;- 24 - ;infrared transmittance (TSIR) of about 20 percent or less and a total solar energy transmittance (TSET) of about 30 percent or less. ;It is expected that the spectral properties of the glass . compositions disclosed herein will change after tempering the glass and 5 further upon prolonged exposure to ultraviolet radiation, commonly referred to as solarization. In particular, it is believed that tempering and solarization of the glass compositions disclosed herein will increase the LTA and reduce the TSUV, TSIR and TSET. As a result, in one embodiment of the invention, a glass composition may have selected spectral 10 properties that initially fall outside the desired ranges previously discussed but fall within the desired ranges after tempering and/or solarization. ;Glass made by the float process typically ranges from a sheet thickness of about 1 millimeters to 10 millimeters. For vehicle glazing 15 applications, it is preferred that the glass sheets having a composition and spectral properties as disclosed herein have a thickness within the range of 0.071 to 0.197 inches (1.8 to 5 mm). It is anticipated that when using a single glass ply, the glass will be tempered, e.g. for an automotive side or rear window, and when multiple plies are used, the 20 glass will be annealed and laminated together using a thermoplastic adhesive, such as polyvinyl butyral. ;It is contemplated that vanadium may be used as a partial or complete replacement for the chromium in the glass compositions of the present inventions. More specifically, vanadium, which is expressed 25 herein in terms of V205, imparts a yellow-green color to the glass and absorbs both ultraviolet and infrared radiation at different valence states. It is believed that Cr203 in the range of about 25 to 800 PPM discussed above may be completely replaced by about 0.01 to 0.32 wt..% *V2057 i J - -' .1 " ____ 32822? As discussed earlier, other materials may also be added to the glass compositions disclosed herein to further reduce infrared and ultraviolet radiation transmission and/or control glass color. In particular, it is contemplated that the following materials may be added to the iron, 5 cobalt, selenium, chromium and titanium containing soda-lime-silica glass disclosed herein: As should be appreciated, adjustments may have to be made to the basic iron, cobalt, selenium, chromium and/or titanium constituents to 15 account for any coloring and/or redox affecting power of these additional materials.

Other variations as are known to those skilled in the art may be resorted to without departing from the scope of the invention as defined by the claims that follow.

MnOz Sn02 ZnO 0 to 0.5 wt.% 0 to 2 wt. % 0 to 0.5 wt.% Mo Ce02 NiO 0 to 0.015 wt.% 0 to 2 wt.% 0 to 0.1 wt.% 328222

Claims (51)

WHAT WE CLAIM IS:

1. A green colored, infrared and ultraviolet radiation absorbing glass article having a composition comprising a base glass portion 5 comprising: Si02 about 66 to 75 percent by weight, NazO about 10 to 20 percent by weight, CaO about 5 to 15 percent by weight, MgO 0 to about 5 percent by weight, 10 Al203 0 to about 5 percent by weight, K20 0 to about 5 percent by weight, and a solar radiation absorbing and colorant portion consisting essentially of: total iron about 0.60 to 4 percent by weight, 15 FeO about 0.13 to 0.9 percent by weight, CoO about 40 to 500 PPM, Se about 5 to 70 PPM, Cr203 about 15 to 800 PPM, and Ti02 about 0.02 to 1 percent by weight, 20 the glass having a luminous transmittance (LTA) of up to about 60 percent.

2. The article as in claim 1 wherein the glass has a redox of about 0.2 to 0.4. 25

3. The article as in claim 1 wherein the glass has a total solar ultraviolet transrrdttance (TSUV) of about 40 percent or less, a total solar infrared transmittance (TSIR) of about 45 percent or less and a total i solar energy transmittance (TSET) of about 50 percent or less. 2 - jy^ 328222 - 27 -

4. The article as in claim 3 wherein the glass has a total solar ultraviolet transmittance (TSUV) of about 35 percent or less, a total solar infrared transmittance (TSIR) of about 40 percent or less and a total

5. The article as in claim 1 wherein the color of the glass is characterized by a dominant wavelength in the range of about 480 to 565 nanometers and an excitation purity of no higher than about 20 10 percent.

6. The article as in claim 5 wherein the color of the glass is characterized by a dominant wavelength in the range of about 485 to 515 nanometers and an excitation purity of no higher than about 10 15 percercL.

7. The article as in claim 6 wherein the color of the glass is characterized by a dominant wavelength in the range of about 490 to 510 nanometers and an excitation purity of no higher than about 7 20 percent.

8. The article as in claim 5 wherein the color of the glass is characterized by a dominant wavelength in the range of about 535 to 565 nanometers and an excitation purity of no higher than about 10 25 percent. 5 solar energy transmittance (TSET) of about 45 percent or less.

9. The article as in claim 8 wherein the color of the glass is characterized by a dominant wavelength in the range of about 540 to ^ " JUL M? 328 2 2 ? - 28 - 560 nanometers and an excitation purity of no higher than about 5 percent.

10. The article as in claim 1 wherein the glass has a luminous 5 transmittance of less than 20 percent at at least one thickness in the range of 1.8 to 5.0 mm.

11. The article as in claim 1 wherein the glass has a luminous transmittance of 20 to 60 percent at at least one thickness in the range 10 of 1.8 to 5.0 mm.

12. The article as in claim 1 comprising a flat glass sheet.

13. The article as in claim 12 wherein said sheet has traces of 15 tin oxide in a surface portion.

14. A green colored, infrared and ultraviolet radiation absorbing glass article having a composition comprising a base glass portion comprising: 20 Si02 about 66 to 75 percent by weight, Na20 about 10 to 20 percent by weight, CaO about 5 to 15 percent by weight, MgO 0 to about 5 percent by weight, Al203 0 to about 5 percent by weight, 25 K20 0 to about 5 percent by weight, and a solar radiation absorbing and colorant portion consisting essentially of: total iron 1 to less than 1.4 percent by weight^ i 2 - n, FeO about 0.2 to 0.6 percent by weight/ ~ tin/ 328222 10 15 20 25 - 29 - CoO greater than 200 to about 500 PPM, Se about 5 to 70 PPM, Cr203 greater than 200 to about 800 PPM, and Ti02 0 to about 1 percent by weight, the glass having a luminous transmittance (LTA) of up to about 60 percent.

15. The article as in claim 14 wherein the glass has a redox of about 0.2 to 0.4.

16. The article as in claim 14 wherein the glass has a total solar ultraviolet transmittance (TSUV) of about 40 percent or less, a total solar infrared transmittance (TSIR) of about 45 percent or less and a total solar energy transmittance (TSET) of about 50 percent or less.

17. The article as in claim 16 wherein the glass has a total solar ultraviolet transmittance (TSUV) of about 35 percent or less, a total solar infrared transmittance (TSIR) of about 40 percent or less and a total solar energy transmittance (TSET) of about 45 percent or less.

18. The article as in claim 14 wherein the color of the glass is characterized by a dominant wavelength in the range of about 480 to 565 nanometers and an excitation purity of no higher than about 20 percent.

19. The article as in claim 18 wherein the color of the glass is characterized by a dominant wavelength in the range of about 485 to 515 nanometers and an excitation purity of no higher than about 10 percent. o ii ~ JUL toy? 328222 -30

20. The article as in claim 19 wherein the color of the glass is characterized by a dominant wavelength in the range of about 490 to 510 nanometers and an excitation purity of no higher than about 7 percent.

21. The article as in claim 18 wherein the color of the glass is characterized by a dominant wavelength in the range of about 535 to 565 nanometers and an excitation purity of no higher than about 10 10 percent.

22. The article as in claim 21 wherein the color of the glass is characterized by a dominant wavelength in the range of about 540 to 560 nanometers and an excitation purity of no higher than about 5 15 percent.

23. The article as in claim 14 wherein the glass has a luminous transmittance of less than 20 percent at at least one thickness in the range of 1.8 to 5.0 mm. 20

24. The article as in claim 23 wherein the FeO concentration is from about 0.22 to 0.5 weight percent, the CoO concentration is greater than 200 to about 450 PPM, the Se concentration is about 10 to 60 PPM, the Cr203 concentration is about 250 to 400 PPM, and the Ti02 25 concentration is about 0.02 to 0.5 weight percent.

25. The article as in claim 24 wherein the FeO concentration is from about 0.3 to 0.5 weight percent, the CoO concentration is greater 2 ~ ml m 328222 - 31 - than 200 to about 350 PPM, the Se concentration is about 35 to 50 PPM, and the Cr203 concentration is about 250 to 350 PPM.

26. The article as in claim 24- wherein the glass has a total solar 5 ultraviolet transmittance (TSUV) of about 30 percent or less, a total solar infrared transmittance (TSIR) of about 35 percent or less and a total solar energy transmittance (TSET) of about 30 percent or less.

27. The article as in claim 26 wherein the glass has a total solar 10 ultraviolet transmittance (TSUV) of about 12 percent or less, a total solar infrared transmittance (TSIR) of about 20 percent or less and a total solar energy transmittance (TSET) of about 20 percent or less.

28. The article as in claim 24 wherein the color of the glass is 15 characterized by a dominant wavelength in the range of about 480 to 565 nanometers and an excitation purity of no higher than about 20 percent.

29. The article as in claim 28 wherein the color of the glass is 20 characterized by a dominant wavelength in the range of about 540 to 560 nanometers and an excitation purity of no higher than about 5 percent.

30. The article as in claim 14 wherein the glass has a luminous 25 transmittance of 20 to 60 percent at at least one thickness in the range of 1.8 to 5.0 mm.

31. The article as in claim 30 wherein the FeO concentration is r from about 0.25 to 0.4 weight percent, the CoO concentration is greater 328 2 2 2 - 32 - than 200 to about 250 PPM, the Se concentration is about 10 to 30 PPM, the Cr203 concentration is greater than 200 to about 250 PPM, and the Ti02 concentration is about 0.02 to 0.5 weight percent. 5

32. The article as in claim 31 wherein the glass has a total solar ultraviolet transmittance (TSUV) of about 35 percent or less, a total solar infrared transmittance (TSIR) of about 40 percent or less and a total solar energy transmittance (TSET) of about 45 percent or less. 10

33. The article as in claim 32 wherein the glass has a total solar ultraviolet transmittance (TSUV) of about 20 percent or less, a total solar infrared transmittance (TSIR) of about 15 percent or less and a total solar energy transmittance (TSET) of about 25 percent or less. 15

34. The article as in claim 31 wherein the color of the glass is characterized by a dominant wavelength in the range of about 480 to 565 nanometers and an excitation purity of no higher than about 20 percent. 20

35. The article as in claim 34 wherein the color of the glass is characterized by a dominant wavelength in the range of about 490 to 510 nanometers and an excitation purity of no higher than about 7 percent. 25

36. The article as in claim 14 comprising a flat glass sheet.

37. The article as in claim 36 wherein said sheet has traces of tin oxide in a surface portion. toil? l c L 328222 - 33 -

38. A green colored, infrared and ultraviolet radiation absorbing glass article having a composition comprising a base glass portion comprising: Si02 about 66 to 75 percent by weight, 5 . Na20 about 10 to 20 percent by weight, CaO about 5 to 15 percent by weight, MgO 0 to about 5 percent by weight, Al203 0 to about 5 percent by weight, K20 0 to about 5 percent by weight, 10 and a solar radiation absorbing and colorant portion consisting essentially of: total iron greater than 0.7 to about 2 percent by weight, FeO about 0.13 to 0.6 percent by weight, CoO greater than 200 to about 300 PPM, 15 Se 5 to 70 PPM, Cr203 greater than 200 to about 300 PPM, and Ti02 0 to about 1 percent by weight, the glass having a luminous transmittance (LTA) of 20 to 60 percent at a reference thickness of 4.06 mm. 20

39. The article as in claim 38 wherein the total iron concentration is from about 0.8 to 1.5 weight percent, the FeO concentration is from about 0.14 to 0.43 weight percent, the CoO concentration is greater than 200 to about 250 PPM, the Se 25 concentration is about 8 to 60 PPM, the Cr203 concentration is greater than 200 tc about 250 PPM, and the Ti02 concentration is about 0.02 to 0.5 weight percent. 328 2 2 2 -34 -

40. The article as in claim 38 wherein the glass has a total solar ultraviolet transmittance (TSUV) of about 35 percent or less, a total solar infrared transmittance (TSIR) of about 40 percent or less and a total solar energy transmittance (TSET) of about 45 percent or less.

41. The article as in claim 38 wherein the color of the glass is characterized by a dominant wavelength in the range of about 480 to 565 nanometers and an excitation purity of no higher than about 20 percent.

42. The article as in claim 41 wherein the color of the glass is characterized by a dominant wavelength in the range of about 490 to 510 nanometers and an excitation purity of no higher than about 7 percent.

43. The article as in claim 38 wherein the glass has a redox of about 0.2 to 0.4.

44. The article as in claim 38 comprising a flat glass sheet.

45. The article as in claim 44 wherein said sheet has traces of tin oxide in a surface portion.

46. A green colored, infrared and ultraviolet radiation absorbing glass article having a composition comprising a base glass portion comprising: Si02 about 66 to 75 percent by weight, /• /< > "v.,, Na20 about 10 to 20 percent by weighj^ >> ^ CaO about 5 to 15 percent by weight. . • 3 2 8 2 2 2 - 35 MgO 0 to about 5 percent by weight, Al203 0 to about 5 percent by weight, K20 0 to about 5 percent by weight, and a solar radiation absorbing and colorant portion consisting essentially 5 of: total iron 0.9 to 1.3 percent by weight, FeO 0.25 to 0.40 percent by weight, CoO 80 to 130 PPM, Se 8 to 15 PPM, 10 Cr203 250 to 350 PPM, and Ti02 0.1 to 0.5 percent by weight, the glass having a luminous transmittance (LTA) of 25 to 40 percent.

47. The article as in claim 46 wherein the total iron 15 concentration is from about 1.083 to 1.11 weight percent, the FeO concentration is from about 0.306 to 0.35 weight percent, the CoO concentration is 90 to 128 PPM, the Se concentration is about 10 to 12 PPM, the Cr203 concentration is 286 to 302 PPM, and the Ti02 concentration is 0.194 to 0.355 weight percent. 20 25

48. The article as in claim 47 wherein the glass has a total solar ultraviolet transmittance (TSUV) of about 25 percent or less, a total solar i..frared transmittance (TSIR) of about 20 percent or less and a total solar energy transmittance (TSET) of about 30 percent or less.

49. A green colored, infrared and ultraviolet radiation absoriw^gV>"%^ glass article having a composition comprising a base glass portion comprising: 32 8 2 22 - 36 - m Si02 about 66 to 75 percent by weight, Na20 about 10 to 20 percent by weight, CaO about 5 to 15 percent by weight, MgO 0 to about 5 percent by weight, 5 Al203 0 to about 5 percent by weight, K20 0 to about 5 percent by weight, and a solar radiation absorbing and colorant portion consisting essentially of: total iron about 0.6 to 4 percent by weight, 10 FeO about 0.13 to 0.9 percent by weight, CoO about 40 to 500 PPM, Se about 5 to 70 PPM, Ti02 about 0.02 to 1 percent by weight, Cr203 0 to about 0.08 percent by weight, 15 v2o5 0 to about 0.32 percent by weight, Mn02 0 to about 0.5 percent by weight, SnOz 0 to about 2 percent by weight, ZnO 0 to about 0.5 percent by weight, Mo 0 to about 0.015 percent by weight, 20 Ce02 0 to about 2 percent by weight, NiO 0 to about 0.1 percent by weight, 25 wherein the sum of the Cr203 concentration plus 25 percent of the V205 concentration is at least 0.0015 percent by weight, and the glass has a luminous transmittance (LTA) of up to 60 percent.

50. A green colored, infrared and ultraviolet radiation absorbing glass article having a composition comprising a base glass portion comprising: / < - 37 - Si02 about 66 to 75 percent by weight, Na20 about 10 to 20 percent by weight, CaO abou'c 5 to 15 percent by weight, MgO 0 to about 5 percent by weight, Al203 0 to about 5 percent by weight, K20 0 to about 5 percent by weight, and a solar radiation absorbing and colorant portion consisting essentially of: total iron 1 to less than 1 .4 percent by weight, 10 FeO about 0.2 to 0.6 percent by weight, CoO greater than 200 to about 4-50 PPM, Se about 5 to 70 PPM, Ti02 0 to about 1 percent by weight, Cr203 0 to about 0.08 percent by weight, 15 v2o5 0 to about 0.32 percent by weight, Mn02 0 to about 0.5 percent by weight, Sn02 0 to about 2 percent by weight, ZnO 0 to about 0.5 percent by weight, Mo 0 to about 0.015 percent by weight, 20 Ce02 0 to about 2 percent by weight, NiO 0 to about 0.1 percent by weight, wherein the sum of the Cr203 concentration plus 25 percent of the V205 concentration is at least 0.0200 percent by weight, and the glass has a luminous transmittance (LTA) of up to 60 percent. 25

51. An article according to any one of claims 1, 14, 38, 46, 49 and 50 and substantially as herein described with reference to any embodiment disclosed. agents 1 3 fU 1988 ' 1 PAR,< * *0N , END OF CLAIMS ^